Gas turbine cycle employing secondary fuel as a coolant, and utilizing the turbine exhaust gases in chemical reactions



June 24, 1958 H. RosENTH-AL'. 2,839,892

GAs TURBINE oycLE EMPLOYING SECONDARY FUEL As A COOLA'NT, AND UTILIZINGTHE TURBINE EXHAUST GASES IN CHEMICAL REACTIONS Original Filed Oct. 4,1947 United States Patenti' ffice GAS TURBINE CYCLE EMPLOYING SECONDARYFUELVAS A COOLANT, `AND UTILIZING THE TURBINE EXHAUST GASES 1N CHEMICALRE- ACTIONS l Henry Rosenthal, Yonkers',

Original application October 4, 1947, Serial No. 778,001, now Patent No.2,660,032, dated November 24, 19S 3. Divided and this application August31, 1953, Serial No. 377 ,292l

is anims. (ci. sol-39.05)

My invention relates V to improvements in gas turbine l 2,839,892.Patented June .24, 1958 l ofthe hydrocarbon fuel.` Inthismanner,saturated hyj drocarbons of the parafiine series may be converted intoolenes and di-oleiines. This reaction is favored by the use of boronfluoride asagaseous catalyst. It will be noted that at thetemperaturesutilized in Ymy turbine cycles and more particularly to gasv turbinecycles in which valuable chemical by-products maybe recovere'dfrom 'theexit gases of the turbine. lThis is a division of my Patent 2,660,032,issued November 24, 1953.

Due tothe present state Lof the metallurgical art, the temperature ofthe gases entering gas turbines, 'as now operated, must be limited tothe maximum temperature that can .be safely handledwith .thernetals asnow used in'the turbine construction. .This temperature` is nowcontrolled by burningthe heating lfuel 'with a portion of thev total airadmittedt'o the combustion ,chamber and admitting suicient secondary airto reduce the teniperature of the productsof combustionto thaty whichcan be safely utilized by the turbine. yThis temperature is from l000 F.to about 2000 ;Fdepending`up'on the turbine construction. A I havediscovered that the 'temperatureof'the turbine can be controlled bytheaddition or excess fuel orlb'y some heat absorbing reaction,'f insteadof by the addition of excess air, and'that when thel temperature is sovcontrolled, valuable oxidation products may be recovered from theturbine exhaust.` Moreover, the yield ofv such by-products is greaterthan'can be obtained by other methods of direct oxidation, so far as Iam aware. This may be explained by the rapidity with which thecombustion products are cooled by adiabatic expansion in *the turbine,particularly if a turbine of the impulse type is used. However, myinvention i's'ap'plicable both to the impulse and reaction typeturbines, as either type will give quicker cooling throughout the massof the gaseous products than obtained by other procedures. Inthe1impulse turbine, this cooling will be from 1/10 to 1/2 millisecond,and in a reaction turbine, it will be from 1 toll milli-seconds. (Thiscompares to approximately 20 to 100 nulli-seconds inthe usual internalcombustion engine.) This quick cooling acts to prevent the oxidation ofvhydrocarbons of a type resulting principally in the formation of carbonmonoxide, carbon dioxide, and Water vapor. Instead, the intermediateproducts of combustion can be retained, and, depending'on the'temperatures,l the contact time, the fuel used, the relative quantityloi-fuel to air, the operating pressure, and onrthe catalysts selectedin the combustion chamber, various productscan be manufactured and canbe recovered from the exhaust gases. 'Some of the products that can bethus obtained are alcohols, esters, aldehydes, ketones, vacidVanhydrides, organic acids, carbon black, etc. Also, if relatively heavyhydrocarbons, such as straw oil or gas oil, are used as fuel, the cyclecan be operated to crack the excess fuel used for temperature control,andihigh vgrade motor: fuel can be recovered from the turbine exhaust.The cycle is also applicable to the dehydrogenationof paratlines.

The oxidizing agent may be air, oxygen-enriched air, or substantiallypure oxygen. Which of these is used will depend upon the particularcircumstances, the materialv to be oxidized, and the reaction productsdesired. Also,

cycle, the boron lluoride will ynotube `unduly corrosive, but caremustbe takento prevent corrosionfafter ,the gases have .left the turbineandthe temperature is reduced, y Other gaseous catalysts may be usedAwith my cycle, depending'upon ythe Idesired ,end product. Thus, nitricoxide (NO),V nitrogen tri-oxide (N203) and nitrogen tetra;

oxide (N294) may be usedto catalyze oxidation reactions.

It willbe noted that some of these materials will be formed'in the hightemperature zone of combustion, through `the interaction Vof thenitrogen and the oxygen A of fthe air, when air', is Vused astheoxidizing medium.

Some of these products will persist throughout the turbine, andnappreciable quantitiesfwill remain Where the time from vthe/primarylcombustion zone to the turbineienl trance is short, thus preventingreversion of the oxides to oxygen and nitrogen before; the quickcooling:.inI the turbine acts to deter the reversion; r y

`vOther gaseous catalysts lare hydrouoric acid, and formaldehyde. Thelatter acts to, speed -the oxidation of aliphatic hydrocarbons intointermediate oxidation products. f f

The objects of my invention are thus, in a gas turbine cycle tov (l)Obtain higher over-all rthermal efficiency than 'is obtained in a usualair cycle, Awhichconsists essentially of ani adiabatic compressiom,anjisopiestic compression, an `adiabatic expansion, and an isopiesticexpansion and in-'wliiclithe temperature attained in the isopiesticcompression lis controlled byfadmission .of excess lair.

(2)7 Produce useful products vof reaction 'othervthan those of completecombustion together withthey generation ofy power.

(3) Produce synthetic chemicals as a .by-product of'A power generation.Other-objects will be apparent froml Y this specification. Y

f Prafne hydrocarbons, either straight or branchedchain, olefine's,benzene, toluene, xylene, andv other hy! drocarbons may beused as thematerial to be oxidized, dependingupon the'desired products. p i 1 Thereaction of'paraiiin hydrocarbons to produce aldehydes ltypified by "thefollowing reactions:

terial ,tobe oxidized is gaseous, some portion of the'v exhaust must bevented from the system in order to prevent an excess build-up lofnitrogen in the system. The. gases so vented will be suitable vfor usein-iiring boilersand for other purposes. The use of oxygen-enriched airwill reduce the amountof venting required, and the 'A substantiallypureoxygen will materially Yreduce i i w( the need for venting. f

If the hydrocarbon oxidized contains three or more carbon atoms and ifthe operating temperaturesareheld within 'such'- limitssovtha't theamountofvcraclring to gaseous products islirnited with relation. to the:amount of' material oxidized, the fuel VVin the j exhaust' may bereadily separated from the nitrogen Vby known methods whenair oroxygenenriched air is used as the'oxidizing medium.v` The nitrogen4could be recovered and further puriedfor otherchernical uses, such asthe manufacture of'` ammonia, if desired. However, the use ofjsubstantially. pure oxygen has certain advantages inthe turbine cycle aswill be explained. e V"When air. or oxygen-enriched air is used as theoxidizingagent, materials rnust be compressed to the inietpressure ofthe turbine. Thework required for this compression utilizes an,appreciable portion of ythe work generatedin the turbine. Ifsubstantially pure oxygen, injt'he liquid state, is used 'for oxidation,the required pressurescan be generated without gaseous compression.'Thisis particularly advantageous where thel higher hy'l drocarhons areoxidized, Aas these can be brought'up to or in;some'ca ses, byapplication of heat tothe liquid, thus' entirelyeliininating thenecessity for gaseous' compression." Unleithisv condition the grossenergy delivered from the turbineis substantially the net energy ofthe Y.The above factors will enter into the cycle when producing 'othermaterials than aldehydes, as described above,a s for instance,intheproduction of alcohol, ac-

cording lto the following equations:

Thereactions take placev at temperatures in excess of 750 YF.; and arefavoredby the use of high pressures. This wouldV require thefuse' ofcompression v,in stages where gaseous fuel isV used in combination withair. However, if the fuel vhas three or more carbon atoms, and oxygen,initially liquid, is used to support the combusti'on, any pressurerequired as favorable to the production of the alcohols, can readily beobtained without the necessity of gaseous compression, which, as hasbeen'explained, results in greater net energy output frontl t l1e-turbine cycle. The alcohol reactions are favored, not only by highpressures, `but also by the presence of catalysts, including 'alum' umoxides, chromates and certain other oxides, and some metals. Theproduction of ethers, 1ikethe production of` alcohols, is favored 4byhigh pressures.r 4The following: reactions typify thewcycle when ethersare the desired by-product:

The production of carbon black in the'turbine cycle,V

perature is carried out at plus 1800 F., the carbon black reaction maybe brought practically to completion in ac" cordance the followingreactions:

C3H 3C|4H2 Similar reactions occur if hydrocarbons of higher molecularweight are used in the cycle. The use of methane leads to the productionof a reinforcing type of carbon black. The use of the higherhydrocarbons leads to the production of a soft type of carbon black. Inorder to provide heat for the above reactions, an oxidation asillustrated by the following equations, takes place substantiallysimultaneously with the reactions leading to the formation ofl carbon.

Similar reactions occur used as fuel.

At lower temperatures than are desirable for carbon formation, vheavypetroleums c'an be introduced into the combustion'chamber of myturbinecycle, preferably as a'ne spray, a'iidlighter liquidhydrocarbons, such as gasoline, 'will b'formed. An inlet temperature of750 ther-required pressure by pumping them in a Hquidphase F. to 110()ovF. at vthe turbine inlet is conducive to this reaction. Like`the'reac'tion for carbon formation, a portion of the fuel is combinedwith oxygen to supply the heat energy. Also, a single stage compressormay be used for compression, if air is used as the oxidizing medium. In'order to hold the lower temperatures desired,

a larger weight ratio ofA fuel to air is required for usualhydrocarbons'cracking than is required for ca rbon black formation.AUnlike the` cracking to carbon black, this reaction does not go tocompletion, so that recovery and recycling of the unreacted fuel will berequired when my cycle is operated withA heavy hydrocarbon fuel for therecovery of motor fuel. Various catalysts known in theart may be used,depending upon the characteristics thatare'desired in the motor fuelrecovered.

`.It vwill be understood that simultaneously with reactions similar tolEquations 1 to 11 inclusive, reactions similar to 15 and 16 may takeplace in or near the zone of prmaryoxidation prior to the addition ofthe excess combustible. This will result in secondary reactions in thesecondary vzone which may be exemplified as follows:

and synthesis f hydrocarbons may be promoted. The principal reactionmaybe predetermined by proper selection of the temperature, time in theprimary and secondary reaction zones, relative vamounts of oxygen andoxidzable substances, and presence of some particular catalyst'. i Itwill further be vunderstood that the above examples are illustrativeonly, as under proper conditions, the reactions can be carried out toresult in other oxidation products, depending on the factors cited inthe preceding paragraphs and `upon the Vcharacter of the oxidizablesubstance utilized. Also, some lesser amounts of other oxidationproducts in addition to the main product desired, will be obtainedsimultaneously with the main reactions, except in such instances as thesubstances may be reacted to substantial completion in a single cycle,as for instance, the reaction tocarbon black. YThis will not appreciablyalfect the value of my process, as these products will have commercialvalue, and in most instances, they may be readily separated from themain desired product.

,In certain instances, itmay be desirable to supply more nS than onefuel (hydrocarbon)` to the` system. Suchga con-l dition'would occurunder the following circumstances: Q (a) when heavy hydrocarbons-areVintroduced for cracking to motor fuels as previously described. Here,the furnace fuel is itself a mixture of various chemical sub# stanceswhich may include recycled products.

(b) when it is desired to obtain'a vspecific chemical through theoxidation and interaction of two substantially pure'hydrocarbons, as forexample in the formation of a mixed ether. r y

(c) when a specified product requires the use of a relativelyexpensivefhydrocarbon for its formation and it is desired to limit theuse of this relatively expensive material in so far as is possible.

As an example of the latter condition, methene may be reacted withoxygen in -accordance withEquations l and 16 and vapors of naphthalenemay be separately introduced into the furnace as a coolant for thereaction products of the methane combustion. If the proper conditionsare maintained in the furnace, the naphthalene may be converted intophthalic anhydride by reactions whichinclude those shown by thefollowing equations:

In a further modification of my cycle, the fuel may be reacted withoxygen in the primary zone of the furnace and the temperature of theproducts of combustion may be lowered by the introduction of steam or awater spray in the secondary zone in the furnace along with additionalfuel. In the primary zone, the reactions are typified by (1'5) CH4+OTCO+H2+H20 (16) CHM-202 0024-211120 In the secondary zone the reactionsmay be typified by the following equations: v

(25) CHHFHZOcarat-1244120Coi-3H2 (26) CH4+Co2-c+2H2+Co2- .9130+2112 (27)CHrl-Z'Hao Cori-4112 Equations 25, 26, and 27 are favored bytemperaturesy in excess of l500 F. and Equations 25 and 27 are furtherfavored by the presence of excess steam. These three equations representendothermic reactions which assist in cooling the products of Equationsl5 and 16 from the high temperatures attained from those latterreactions to the temperature required at the turbine inlet. In thepassage through the turbine, these gases are so quickly cooled by theadiabatic expansion, as to prevent exother'mic reversion of the carbonmonoxide and hydrogen to carbon and Water or to carbon and carbondioxide. However', the temperature of the gases leaving the turbine issuiciently high to promote the FischerTropsch synthesis in the presenceof a suitable catalyst. This latter reaction may be typified by thefollowing equations:

delivered vtothe system and fed to the combustion'chamber as a. vapor orspray, as inthis' case the gross'power from the turbine 'issubstantially i the net `power of the cycle. This is due to the Vfactthat the lcompressor is eliminated. t n v The hot products leaving theturbine exhaust maybe brought into heat exchange with'therelatively'cool lrnaterials entering the combustion chamber, and againin thermal efficiency of the cycle will result. Heating of thematerial to the combustion chamber by heat exchange with the hot'exhaust gases is particularly-desirable where liquid materials are usedlas fuel andare deliveredto the combustion chamber either asa spray ora'vapor.- Where the gases leave the turbine? ata temperature'of fromf950F. to l350 F., Yhydrocarbonsmaylbeintroduced into the stream.Theintroduction of hydrocarbons having a molecular weight above 44, intothe stream at these temperatures, will lead to theircracking..rRelatively light hydrocarbons, such as` butane, may be introduced asa'vapor and heavy hydrocarbons such'as straw-oil may be introduced as aspray. i 1

My invention may best be described by reference Ltothe followingdrawings, in which Y Fig. l illustrates diagrammatically, my inventionas applied to the productionof formaldehyde# 4 Fig. 2 similarlyillustratesrny invention as applied to the formationfof carbon black. n'"i f Fig. 3 diagrammatically illustrates my inventionas applied to theproduction of motor fuel thru the synthesis from carbon monoxide andhydrogen. Y v 4 It will be recognized thatthese examples are-merelyillustrative of my invention, as slightly different diagrams may bedesirable for the production of other products than formaldehyde, carbonblack, or motor fuel. YAlso for the production of formaldehyde orcarbon' black, modifications may be made in the details lof the cyclesillustrated, without departing from the spirit of my invention. Thiswill be readily understood by'on'e skilled in the art. l v 't Referringto'Figure l: the air compressor 1, andthe methane compressor 2 aremechanically connectedfto' each other and to gas turbine'3 .and theelectric generator (or other load) 4 by means of the shaft 7. The gasturbine 3 is preferably an impulse typefturbine. Air from the atmosphereentersv thetcompressor 1 by means of pipe 3, and the compressed air-from the compressor 1 is delivered by pipe`9 to the primary `reactionchamber 6 of the furnace 5,'thru enlarged portion' 10and pipe 9. Methaneis delivered zto the compressor 2 by means of the pipe 11 simultaneouslywith return gas'by means of the pipe 22, as will be explained later.''The compressed gas is delivered tothe primary lreaction chamber 6 ofthe furnace 5 by means' of pipes I2 and 13, and to the secondaryreaction chamber 26 of' the-"furnaceV 5 by means of pipes 12 and 14. Theenlarged portion 10 of pipe 9 permits the pipe 13 to be p lacedwithinhestream of incoming air so that Ythe combustible is sur` rounded by airas thevtwo are delivered tothe primary reaction chamber. Gas from thesecondary chamber 26 may also enter the primary chamber 6 by the ports15 in the partition V27 vseparating the `secondary chamber from theprimary chamber. The partition 27 y and the furnace 5 are preferablymade of chromium upon which a layer of oxide has been built up toassistgin ythe conversion to formaldehyde. primary chamber is adjustedto maintain continuousignition of the methane. n The quantity of methaneaddedin the secondary chamber is adjusted to reduce ythe tem.

perature of the combustion products entering the turbine to the desiredamount and to promote the desired reaction. The heated gas, afterreaction, is led,t`o the turbine 3 by means of the pipe 16. In theturbine, the gas is expanded while doing work, which effectively:reduces the temperature to an amount which substantially preventsfurther chemical reactions in theg'as stream. The ex-A panded gas isledfrom'the turbine S'by' the pipe 417"tok The ratio ofl gas toair inthe` fi? the recovery system 18 which, in this instance is shown as ,acountercurrent scrubber, to whichcold water or other absorbent is;introduced thru the pipe 24 and the solution of formaldehyde s removedby the pipe 25 to` any suitable formof concentration system (not shown).The scrubbed. gas, substantially free from formaldehyde, is withdrawn,from the scrubber 18 by the pipes 19 and 20 tothe gas holder 21, fromwhich it may be withdrawn by pipes 20 and vZ2 and returned tothecompressor 2 or by pipe23by which it is withdrawn from thesystem. Toprevent'an'excessive buildup of nitrogen which is introduced into thesystem in air thru pipe 8, somewithdrawal must be made ofthe reactedgases thru Vpipe 23. If there are other uses for heating gas, all of thegas rejected byr the scrubber 18 may be withdrawn from the system by thepipe 23. In this instance, no methane would be delivered tofthecompressor 2 by the pipe 22, andthe entire supply of methane would bedelivered to the system by the pipe 11. The following example is basedupon the latter operation as computed for possible yields:

Temperature of air to compressor 60 F.=520 R. Temperature of methanerto4crompres- Y sor V 607 F.=520 R. Pressure at compressor inlet 15 p. Vs.i.-abs. Pressure at compressoroutlet 90 p. s. i.-abs. Temperature ofgasentering turbine 1500 F =1960 R. Temperature of gas leaving nozzle825 F Temperature.. of gas leaving turbine 1025 F =1485 R. Poundsmethane consumed as fuel per pound methane to the system Pounds of airper pound methane to u system Pounds formaldehyde per pound totalmethane to system Pounds formaldehyde per day per 1000 kw. outputofturbine Total methane per dayk per 1000 kw. voutput (cu. ft.) Consumedmethane penday (asfuel) per 1000 kw. (cu.V ft.) ouput Heating value ofgas ,from scrubber (cu. ft.) Efficiency of turbine cycle, based on heatof combustion of entering methane; less heat of combustion ofvexhaustproducts Etlciency of air cycle turbine having same .temperature andpressure ratios :500 B. t. u. Y

The above data are based upon the use of a well-known single stageimpulse turbine in which the entire adiabatic expansion takes place in asingle stage nozzle placed withinV the turbine immediately following theturbine entrance.

If methyl alcohol were the des'iredproduct, a cycle similar to thatshown in Fig. 1 would be applicable. However, the production of alcoholis favored by higher pressures. The scrubber 18v and holder 21 are thusoperated under pressurei and the pressure of` the furnace 5 and turbine3 is greater than when formaldehyde is the desired product. TheY ratioof methane to air is also adjusted as required.

Referring to Figure 2,`the air and gas compressors 1 and 2, turbine.3,electric generator 4, furnace 5 withl primary `reaction chamber 6 andsecondary reaction chamber k26,"and shaft 7 are the same as has beenexplained'in connection with Fig. 1. Also, pipes 8, 9, 11, 12, 13,14,and 16 are used in the same manner` as scribed figure, 1 Pire-.1,7leads' from .th turPine sxhaust;v to the carbon black` collectingsystem, which is indicated as cooler 31; and as electrostaticprecipitator 28. Pipe29 is used for removing the gas exhausted from theprecipitator. Injthisinstance all the gas is rejected from the cycleafter theremoval of the carbon black by the precipitator. Carbon isremoved from the system by the conveyor 30. In the production of carbonblack, the temperature ofthe furnace is preferably held at approximately1800" F. or in `excess thereof. No catalyst is required for thisoperation as the carbon produced is in itself a catalyst for thereaction to carbon. The following figures are pertinent to4 thisoperation, based on complete methane conversion.

Pounds of air per pound of methane 2.65 Pounds of carbon black producedper thousand cubic feet'of methane to system 23 Cu. ft. of methane perday per 1000 kw. output S300M Poundscarbon black per day per 1000 kw.

output 75,000 Exhaust gas per day per 1000 kw. output (cu. ft.) 11,700MHeating value of gas from precipitator (B. t. u./cu. ft.) 189 Efliciencyof turbine cycle, based on heat of combustion of entering methane lessheat of combustion of exhaust products 62.5%

Referring to Figure 3, the air and gas compressors 1 and 2, turbine 3,electric generator 4, furnace 5, with primary reaction chamber 6 andsecondary reaction chamber 26, andshaft 7, are the same as has beenexplained in connection with Figure 1. However, the steam pipe 33 isprovided in Figure 3 to furnish a source of steam to the secondaryreaction chamber 26. Pipes 8, 9, 11, 12, 13, 14 and 16 are used inFigure 3 in the same manner as 4was described in connection with Figurel.

Pipe 17 leads from the turbine exhaust to the catalytic reaction chamber34, which can be any type of conversion chamber suitable for promotinghydrocarbon synthesis reactions from CO and H2. The gas stream from theconversion chamber 34 passes by conduit 35 to the cooling and separatingsystem 36, in which the readily condensible reaction products areremoved from the stream through conduit 37. The uncondensed gases passfrom the cooling and separating system by the conduit 38. These gasesmay be discharged from the system by conduit 39, or they may bere-circulated back to the system. Thus, they may be led into acompressor 43 by pipe 46, where they are compressed, and led by pipes 40and 41 back'into pipe 17 where they are used to cool the gases from theturbine 3 and are re-circulated back thru reaction chamber 34.V

If compressor 43 is suitable for delivering gas at high pressure, thegases from the separating system 36 may be passed 'back to thecombustion chamber by pipes 38 and 46, compressor 43 and pipes 40 and4S. As an alternative method of controlling the temperature of the gasesentering reaction chamber 34,a cooler 42 may be provided in pipe 17 forconducting gas from the turbine 3 to the reaction chamber 34.

Now, having described my process in a manner that may be readilyunderstood by one skilled in the art, I claim:

1. A process for making valuable products of incomplete oxidation of afluid-fuel in conjunction with the operation of a gas turbine, whichincludes the steps comprising, passing under superatmospheric pressure acombustible fluid to be oxidized as a stream into a primary reactionzone, confined in a reaction chamber, also under superatmosphericpressure passing an oxidant into said zone as a stream, promotingexothermic reactions of said combustible fluid with said oxidant in saidzone at a high temperature, above 2000 F., v passing the hot reactionproducts thus made Adirectly andcontnuously from said F. but above 750zone to a secondary reaction zone of' said chamber, immediately mixingit therein with additional reactants, including steam or water, therebypromoting chemical endothermic reaction in the mixture with theformation =of carbon monoxide and hydrogen while lowering thetemperature of the reacting fluid mixture to below 2000 F. but above 750F., passing the thus cooled reacting mixture immediately into a gasturbine and therein materially reducing the temperature of the lattermixture while simultaneously reducing its pressure, and finally passingthe turbine exhaust gases, containing carbon monoxide and hydrogen intoa reaction chamber in the presence of a catalyst, utilizing the sensibleheat of the turbine exhaust for initiating catalytic reaction.

2. In a gas turbine cycle of a suitably connected gas turbine unit, thesteps comprising passing a stream initially containing a combustiblematerial into the primary reaction zone of the combustion chamber ofsaid unit and substantially completely burning said material therein,thus raising the temperature of said stream above 2000I F., introducingadditional combustible material and steam 'or water into a secondaryreaction zone of said chamber, passing the thus heated stream from theprimary reaction zone into the secondary reaction zone and mixing itwith said additionalcombustible material and steam or water and mixingit therewith, thereby promoting endothermic reactions in said secondaryreaction zone and lowering the temperature of the reacting mixture tobelow 2000 F., then substantially immediately passing the hot reactingmixture into a gas turbine and lowering its temperature by substantiallyimmediate adiabatic expansion, whereby the hot reacting mixture iseifectively cooled, and finally passing the turbine exhaust gases,containing carbon monoxide and hydrogen into a reaction chamber in thepresence of a catalyst, utilizing the sensible heat of the turbineexhaust for initiating catalytic reactions.

3. The cycle described in claim 2 in which the combustible materialintroduced into the secondary reaction zone is `diierent from thecombustible passed into the primary reaction zone. g

4. The cycle described in claim 2 in which the steam or water isintroduced into the secondary reaction zone as a separate stream fromthe additional combustible material.

5. In a gas turbine cycle of a suitably connected gas turbine unit, thesteps comprising, passing a gaseous stream initially containing acombustible material into Vthe primary reaction zone of the combustionchamber of said unit under superatmospheric pressure, promotingsubstantially complete combustion of said material therein to raise thetemperature of said gaseous stream to above 2000 F., introducing asecond stream of combustible material together with steam or water alsounder superatmospherie pressure at a lower temperature than 2000 F. intoa secondary reaction zone of said chamber, passing the thus heated firstmentioned gaseous stream while at a temperature above about 2000 F. intothe secondary reaction zone and mixing it with second stream of materialtherein, thereby promoting endothermic reaction, the rate of feed of,said second stream being so regulated that the temperature of themixture is lowered below about 2000 F., then substantially immediatelypassing thehotj reacting gaseous mixture in the latter temperature rangeinto the turbine of said unit and lowering its 'temperature immediatelyby substantially adiabatic expansion therein, and finally passing theturbine exhaust gases, containing-carbon monoxide and hydrogen, into areaction chamber in the presence of a catalyst, utilizing the sensibleheat of the `turbine exhaust for initiating catalytic reaction. Y

6. The cycle described in claim 5 in which the combustible materialintroduced into the secondary reaction zone is diferent from thecombustible material introduced into the primary reaction zone.

7. The cycle described in claim 5 in which the steam or water isintroduced into the secondary reaction zone as a separate stream fromthe combustible material.v

8. In a gas turbine cycle adapted for thegeneration of power 'in asuitably connected gas turbine unit in which gasiform products ofincomplete oxidation are produced, the steps comprising, continuouslyintroducing under superatmospheric pressure into the reaction zone ofsaid unit both a stream of lfuel and a stream of gasiform uid containingoxygen in such proportion as to supply complete oxidation of said fuel,initiating and promoting oxidation in an oxidationphase, whereby atleast a portion of the fuel is'completely oxidized and the temperatureof the resulting reaction products is raised to above 2000" F.,continuously withdrawing the gas stream of oxidized products from theoxidation phase and substantially immediately passing vsaid gaseousstream into a reduction phase with the addition of a second stream ofcombustible material with steam or water under superatmospheric pressureand a temperature substantially less than 2000" F., whereby the hotproducts from the oxidation phase are cooled and a portion of the highlyoxidized products of the oxidation phase are reduced to lower oxides byreacttons with said second stream, continuously withdrawing the reactingproducts in a gaseous stream from the reduction phase at a temperaturebelow 2000 F., but about 1200 F., and substantially immediatelydischarging said latter lstream into the turbine of said unit andsubstantially adiabatically expanding and cooling it therein, andfinally passing the gases containing hydrogenyand carbon monoxidedischarged from said turbine linto a reaction' chamber in the presenceof a catalyst, utilizing the sensible heat of the turbine exhaust gasesfor initiating catalytic reaction.

9. The cycle described in claim 8 in which the combustible materialintroduced into the reducing phase' is different from the combustiblematerial introduced 'into the oxidizing phase.

10. The cycle described in claim 8 in which the combustible materialintroduced into .the reduction phase is introduced separately from thesteam or water.

1l. In a gas turbine cycle adapted for the generation of power in asuitably connected gas turbine unit, in which gasiform products ofincomplete oxidation are produced, the steps comprising, continuouslyintroducing under superatmospheric pressure into the primary reactionzone of the combustion chamber of said unit both a stream initiallycontaining vapor phase fuel and a stream of gasiform fluid containingfree oxygen, initiating and promoting the complete combustion `of saidstream of fuel in said oxygen containing stream in said zone, the

amount of said oxygen being sufficient for the complete' combustion ofsaid fuel', thereby raising the temperature of the combined streamconsiderably above 2000 F., continuously passing the hot products of thecombustion while under pressure into a secondary rea-ction zone of saidchamber simultaneously introducing a predetermined additional amount ofsaid fuel in a stream under superatmospheric pressure and a temperatureconsiderably -below that of the stream from the primary reaction zoneinto said secondary, reaction zone and mixing it therein with the saidvhot products of the combustion, thereby causing the latter fuel toyreact endothermically with the said products of combustion, loweringthe temperature of the latter, passing the gaseous mixture whilereactions are still occurring therein, into the turbine of said unit andsubstantially adiabatically expanding and cooling it therein, and thenwithdrawing the expanded gaseous products from the turbine andintroducing thereto a iluid hydrocarbon having a molecular weight inexcess of 44, and maintaining said hot gas stream in conta-ct with saidhydrocarbon for sufficient time to promote thermal cracking for aportion of said hydrocarbon.

12. The cycle described in claim ll in which a catalyst is added topromote cracking of the final hydrocarbon addition.

13. `In a gas turbinecycle of a suitablyconnectedgas turbineunit, thesteps comprising, passing ,aggaseous stream initially Vcontaining acombustible material into the primaryvreaction zone of the combustionchamber of said unit under superatmospheric pressure, promotingsubstantially complete combustion of said material therein to raise thetemperature of said gaseousL stream above 2000,v F., introducing asecond stream of combustible material also undersuperatmospheric.pressure ata lower temperaturethan 2000i. F. into asecondaryreaction zone of said chamber, passingthethus heated iirstmentioned gaseous stream while at a temperature above about 2000 F..into said secondary reaction zone and mixing itwith said secondstreamrof combustible material therein thereby promoting endothermicreaction of the latter material in the mixture, the rateof feed of saidsecond stream `being so regulated that the temperature of the mixture islowered below about 2000 F. but above 7 50 F., then substantiallyimmediately passing the hot reacting gaseous mixture in the lattertemperature range into the turbine of said unit and lowering itstemperature immediately by substantially adiabatic expansion therein,whereby the hot reacting mixture is effectively further cooled, and thenwithdrawing the expanded gaseous products from the turbine andintroducing thereto a fluid hydrocarbon having a molecularrweight inexcess of 44, and maintaining said hot gas stream in contact with saidhydrocarbon for suicient time to promote thermal cracking of a portionof said hydrocarbon.

14. The cycle described in claim 13 in which a catalyst is added topromote cracking of the nal hydrocarbon addition. a Y

15. In a gas turbine cycle adapted forthe generation of power in asuitably` connected gas turbine. unit in which gasiform products ofincomplete `oxidation are produced, the steps comprising, continuouslyintroducing under superatmospheric pressure into the reaction zone ofsaid unit both a stream of fuel and a stream of gasiform fluidcontaining oxygen in such proportion as to supply complete oxidation ofsaid fuel, initiating and promoting oxidation in an oxidation phase,whereby at least a portion Vof the fuel is completely oxidized and thetemperature `of the resulting reaction products is raised to above`2000" F., continuously withdrawing the gas stream of oxidized productsfrom the oxidation phase and substantially immediately passing saidgaseous stream into a reduction phase with the addition of a secondstream of combustible material under superatmospheric pressure and atemperature substantially less than 2000 phase are cooled and a portionof the highly oxidized products of the oxidation phase are reduced tolower oxides by reactions with said second stream of combustiblematerial, continuous withdrawing the reacting products in a gaseousstream from the reduction phase at a temperature below 2000 F. 'butabove 1200 F. and substantially immediately discharging said latterstream into the turbine of said unit and substantially adiabaticallyexpanding and cooling it therein, and then withdrawing the expandedgaseous products from the turbine and introducing thereto a Huidhydrocarbonhaving a molecular weight in excess of 44, and maintainingsaid hot gas stream in Contact with said hydrocarbon for suicient timeto promote thermal cracking of a portion of said hydrocarbon.

16. A gas turbine cycle for the generation of power comprising the stepscompressing a gasiform combustion supporting Aiiuid to increase itspressure; passing the thus compressed uid substantially continuouslyinto a combustion chamber while simultaneously a combustible into saidchamber in controlled amounts; promoting substantially completecombustion in said F., whereby the hot products from the oxidationintroducing temperature below 2000 tion; substantially immediatelypassing the reacting gasesubstantially constant sensible heat remainingfrom chamber at`substantially constant pressure to raise `thetemperature of the combustion products above 2000 F.; passingthe thusheated combustion products into a secondary reaction zone undersubstantially the same pressure and simultaneously introducing an amount,of com,- bustible'uid in excess of that required for completecombustion, along with steam or water to reduce the temperature of theresulting stream below 2000 F. in part by endothermic reactions;immediately passing the latter stream from the. substantially constantpressure stage into an expansion stage in which latter stage thereacting gaseousvmixture is expanded with a decrease in pressure,whereby intermediate combustion products formed in the substantiallyconstant pressure stage are quickly cooled adiabatically andfinallypassng the expanded gaseous stream at substantially constantpressure into a reaction chamber in the presence of a catalyst andpromoting catalytic reactions therein utilizing the sensible heatremaining from the expansion stage.

17. A gas turbine cycle for the generation of power comprising thesteps, compressing a gasiform uid containing free oxygen with increasein pressure, passing the. thus compressed fluid substantiallycontinuously vinto a combustion chamber while simultaneously introducinga hydrocarbon fuel into said chamber in controlled amounts, promotingsubstantially complete combustion in said chamber at substantiallyconstant pressure to raise the temperature of the combustion productsabove 2000 F., passing the thus heated combustion products into Va samepressure and simultaneously introducing an amount of hydrocarbon fuel inexcess of that required for complete combustion, along with steam orwater to reduce the ltemperature of the resulting stream below 2000 F.in part by endothermic reactions, immediatelypassing the latter streamfrom the substantially constant pressure stage into an expansion stagein which latter stage the reacting gaseous mixture is expanded with adecrease in pressurey whereby the intermediate combustion productsformed in the substantially constant pressure stage are quickly cooledadiabatically, and finally passing the expanded gaseous stream atsubstantially constant pressure into a reaction chamber in the presenceof a catalyst and promoting catalytic reaction therein utilizing thevsensible heat remaining from the expansion stage.

v18. A gas turbine cycle for the generation of power comprising thesteps of compressing a gasiform fluid with increase in pressure; addingan amount of heat at substantially constant pressure, said heat beingadded by addition of Huid fuel to said gasiform stream in an amountsubstantially required for complete combustion to bring the temperatureof the stream in excess of 2000 F. and then adding an additional amountof fuel and an amount of steam or water in quantities to reduce the F.in part by endothermic reacous mixture from the substantially constantpressure stage into an expansion stage, in which the reacting gaseousmixture is expanded with decrease in pressure whereby the intermediatecombustion products formed in the pressure stage are quicklyV cooledadiabatically and finally passing the product from the expansion stageinto a substantially constant pressure stage in a reaction chamber inand promotingy catalytic reactions therein, utilizing the the expansionstage.

References Cited in the file of this patent UNITED STATES PATENTSsecondary reaction zone under substantially theV the presence of acatalyst@ Rosenthal Nov. 24, 1953

1. A PROCESS FOR MAKING VALUABLE PRODUCTS OF INCOMPLETE OXIDATION OF AFLUID-FUEL IN CONJUNCTION WITH THE OPERATION OF A GAS TURBINE, WHICHINCLUDES THE STEPS COMPRISING, PASSING UNDER SUPERATMOSPHERIC PRESSURE ACOMBUSTIBLE FLUID TO BE OXIDIZED AS A STREM INTO A PRIMARY REACTIONZONE, CONFINED IN A REACTION CHAMBER, ALSO UNDER SUPERATMOSPHERICPRESSURE PASSING AN OXIDANT INTO SAID ZONE AS A STREAM, PROMOTINGEXOTHERMIC REACTIONS OF SAID COMBUSTIBLE FLUID WITH SAID OXIDANT IN THEHOT REACTION TEMPERATURE, ABOVE 2000*F. PASSING THE HOT REACTION PRODUCTTHUS MADE DIRECTLY AND CONTINUOUSLY FROM SAID ZONE TO A SECNDARYREAWCTION ZONE OF SAID CHAMBER, IMMEDIATELY MIXING IT THEREIN WITHADDITIONAL REACTANTS, INCLUDING STEAM OR WATER, THEREBY PROMOTINGCHEMICAL ENDOTHERMIC REACTION IN THE MIXTURE WITH THE FORMATION OFCARBON MONOXIDE AND HYDROGEN WHILE LOWERING THE TEMPERATURE OF THEREACTING FLUID MIXTURE TO BELOW 2000*F.